Production of materials, decorative articles, and protecting linings or the like, bythe transformation of fibrous cellulose materials



Aug- `14, 1934- v. Bosso E-r AL PRODUCTION OF MATERIALS, DECORATIVEARTICLES, AND

PROTECTING LININGS OR THE LIKE, BY THE TRANSFORMATION 0F FIBROUSCELLULOSE MATERIALS Filed July 9, 1932 2 Sheets-Sheet l E Sacchi ATTORNE YS.

' Aug. 14, 1934. VA Boss@ ET AL 1,970,273

PRODUCTION OF MATERIALS, DECORATIVE ARTICLES, AND PROTECTING LININGS ORTHB LIKE, BY THE TRANSFORMATION OF FIBROUS CELLULOSE MATERIALS FiledJuly 9, 1932 2 Sheets-Sheet 2 www 2PM ATTORNEYS. I

Patented Aug. 14, 1934 PRODUCTIUN F MATERIALS, DECORATIVE ARTICLES, ANDPBOTECTING LININGS 0B THE LIKE, BY THE TBANSFURMATION 0F FIBBOUSCELLULOSE MATERIALS Valentino Besso, Nicolo Siivestrlni, and Francesco ySacchi, Torino, Italy, assigner! to Guido Botta,

Paris, France Application July 9, 1932, Serial No. 621,644 In FranceNovember 16, 1931 The invention relates to the production oi materialsfor making decorative articles and protective linings or the like.

It is known that, in the production of objects of a decorative nature,or of articles serving for lining and protecting w iloors, ceilings,furniture and the like, use is sometimes made of sheets, boards,mouldings, or the like, which are :formed by assembling, drying andcompressing 0 brous cellulosic materials, or by other analogous means.

Thus these iibrous materials are commonly employed in the form of sheetsof considerable thickness.

It is known that the iibres composing iibrous cellulose materials arecapable of agglomerating and forming a continuous material, possessingstrength simply by using water as the sole agglomerating agent.

The water separates the fibres in proportion to the volume of wateremployed. The present invention is in part based on the observation thatthe degree of agglomeration of the libres being treated may be regulatedas desired by regulating the quantity of water.

The invention is also based upon the observation that the marbling andveins which are noticeable, for example, in sheets of crude cellulose,such as those that come oi! paper machines. (see Figure 1 of thedrawings) can be exploited from the decorative point of view, on accountof the non-uniform color-absorbing capacity or on account of the simpledifferences in natural color or tone, which they adopt when they undergothe treatment eiected during the second stage of the process set forthbelow.

The marbling, veins or streaks as they generally occur, are notsuiciently pronounced, nor suiiciently decorative. This desireddecorative appearance can be obtained in accordance with this inventionby accentuating and exaggerating the appearance and shape oi' themarbling, veins, etc.

It is an object of'this invention to provide a process which causesmarbling and veining to be produced artiiicially. l

The methods of carrying out this process may diier depending on whetherthey are applied to brous boards in the wet state, in the dry state, ordining drying treatment; but essentially they are all based upon anexaggeration of the mechanical eii'ects which normally tend to producethese breaks in continuity.

The present invention provides a method for 55 producing decorativematerials from cellulose bres in which we can regulate or control thelateral vibrations applied to the screen of a paper machine whileregulating the water supply, so as to eiiect an irregular distributionof the iibres in the sheet to obtain marbling, veins and the like, goodresults having been obtained by .doubling the vibrations per minute ascompared with paper making practice, while keeping the speed oflongitudinal movement of the screen constant. 35

'I'he adjustment ot the water supply may be effected either by employingan excess of water,l or in adding collogenous materials such as adecoction oi linseed to the water employed in the process, for thepurpose of making the mass more '7 viscous. The linseed makes the wateremployed in the process deiinitely colloidal in nature, and veryviscous, so as to render the drying operation diiiicult. Thus, the pasteor pulp which arrives charged with water, particularly in the thickerparts which have been produced in the form or longitudinal thickeningsby the action of the exaggerated vibrations above referred to, is forcedout under the press very suddenly where the veins are situated, and thisincreases the size of the openings at these points.

When the sheet is dried the veins may be still further accentuated ii'the sheet is wound upon itseli', and it, for example, it is subjected toa twisting action at one end in the direction of the 35 axis upon whichit is wound, while keeping the other lend fixed; or ii' it is subjectedto a crum- Apling or creasing action carried out by hand, or

again, if the continuous sheet is made to pass between cylinders whichare not uniformly round, but comprise irregularities of a positivenature on one cylinder, and ofa negative nature on the other cylinderwith the object of producing this crumpling or creasing artiiicially.

Finally, in certain cases the boards may be subjected to the action of apreliminary bath in a solution of van astringent material which by rapiddrying creases or lines the boards.

The second stage of our improved method comprises a gumming operation inwhich we utilize animal gelatine.

This bath is characterized by the fact that a substance containing thegroup SiOz e. g. sodium silicate or silicic acid is incorporated in thegelatine solution. This gives the gumming solution a special'property,the finished product acquiring increased thickness and compactness andincreased waterprootness. n

According to our invention above mentioned substances may beincorporated in the gumming f by soaking the paper and the fabric to begummed previously with the solutions, or by causing these substances tobe formed or liberated inthe bath itself.

The following mode of procedure is given by way of egample only, and isnot limiting in any way.

The gelatine bath is prepared by dissolving 25 kilograms of very'iinedry gelatine in 100 litres of water. The temperature is raised to 50 C.,and if desired, as far as '10 C. When all the gelatine is dissolved aquantity of sodium silicate is added, which may vary in amount from 100grs. to 500 grs. and then 200 grs. of aluminium sulphate or 250 grs. ofordinary alum are added.

It is preferable to add these salts after they have been dissolved inwater.

It is also possible to vary the order in which the substances are added,and add the alum or aluminium sulphate before the silicate.

In place of sodium silicate, potassium silicate and other silicates maybe added, or silicic acid in a suitable form.

The gumming bath after successive periods of agitation and rest isutilized in the usual way, and

the material to be treated may be made to pass through it in sheets, orin continuous rolls, according to the form in which it is employed.

In order to increase the stiffness of the finished material it issufficient simply to increase the proportion of the silicates to about500 grs. or more, the remainder of the operation remaining u nchanged asdescribed above.

As soon as the material has left the bath it is allowed to dry graduallyin a chamber at normal temperature -(about 20 C.) and with a simplecurrent of air for a period of 24. hours.

In addition to the foregoing applicants have found that if the sheet ofmaterial, after leaving the gumming bath, is subjected to a current ofcold air at a temperature around 5 to 10 C. the state of gel which isformed tends to improve the technical properties and the strength of thesheet. The latter when subsequently fixed or tanned behaves better thanwhen treated at ordinary temperature, that is to say, at 20 to 30 C.because with the latter temperatures a wide dispersion of the materialoccurs in the connectigiu between the fibres which compose the sheet iSubsequently the sheets are treated to a fixing and hardening or tanningaction in Va suitable bath, such asa hot. gaseous formaldehyde bath,v.or a cold dilute formaldehyde bath; or a hot 10% bath of potassiumchromate, to which is added 1% of castor oil emulsion; or a chroniicacid bath; or other suitable baths. The material resulting from theaction of the 'gumming bath is more homogeneous from the molecular andchromatic point of view when the drying action is carried out imiformlyand nahxrally.

Naturally the invention also comprises modiilcations in the compositionof the bath, to which. in addition to the materials indicated above,other plastifying may be added, such for example as a rationalproportion of glycerine etc. f

Ifsaltsofthealkalioralkalineearthmetals (e. g. K, Na, Ca) are added tothe gelatine bath.

with other salts, preferably halides, or heavy metals, salts such assalts of tin, aluminium, copper etc., fatty bodies may be readilyincorporated in the form of insoluble soaps of those substances that aresaponiiiable and which have an added waterproofing action while fatty orwaxy substances which do not saponify, are distributed in the mass inthe form of an emulsion.

When the material has been soaked by immersion in the gelatine solutionit is desirable that it be subjected to supplementarycoagulating, orwaterproofing action, by a known process as indicated above, that is tosay, by means of formaldehyde, potassium chromate, chromic acid, or bysimilar substances.

The impregnation of the cellulose material whether in the form ofcardboards, wood pulp, cotton pulp etc., is considerably improved whenthese materials or articles have been previously subjected to a.softening treatment by means of gases or vapours of a suitable nature.

Applicants have found that as a result of this softening action thematerials treated can absorb a much greater quantity of the gummingbath, and retain a greater quantity of gelatine.

` On account of this more intense gelatinization the nished product isimproved by the fact that a more intimate connection exists between thegelatine and the libres, and consequently the outer layer of gum has agreater thickness. When the cellulose material is to be immersed insolutions of animal gelatine acetic acid vapours at high temperature aremost effective for producing this preliminary softening. One method ofapplying the acetic acid vapours may consist in enclosing the cellulosematerials in any suitable form, such as cardboard, linters etc., incontainers or casings having a fluid-tight closure. These containers arethen put into communication with a vacuum machine.

When the maximum possible vacuum has been obtained the communicationbetween the vacuum machine and the container is cut off, and the latteris put into communication with an autoclave apparatus containing aceticacid which has been brought to a state of superheated vapour.Approximately a quarter of an hour after-the communication has beenestablished the atmosphere containing the cardboard, linters etc., hasgenerallybeen completely saturated. This communication is then cut off,and the cardboards and the linters are left for 3 to 4 hours in thissaturated atmosphere.

Finally, air under pressure is admitted at one side of the receptacle.This air Vpasses out at 125 the other side of the receptacle and carriesaway the residue of the acetic vapours.

Cardboards and linters etc., thus prepared, are ready for treatment inone of the gumming baths described above. Subquently, after a uniform130 drying they pass into a tanning or hardening bath as described fortransforming these incorporated materials into a new material, having anew form and character.

In the acco drawings the invention 13E is illustrated, and

Figure 1 shows a plan view of a portion of a continuous sheet ofcellulose as it has left the paper machine;

Fig. 2 shows the same sheet after it has been 14 submitted to torsion ortwisting;

Flg.3showsthesheetinFig.2afterithas again been flattened out;

Fig. 4 shows a similar sheet of cellulose which has been subjected to amechanical crumpling 14 and creasing; and

Fig. 5 shows in end view a pair of cylinders 10 and 11, the surfaces ofwhich are provided with complementary ribs 12 l grooves 13 andbetweeawhichispasseda 14ofcel1ulosefor15 accentuating marbling orconfiguration on the surface of the sheet.

These examples have been given simply for the purpose of indicatingmodes of carrying the proc-v ess into effect. It is clear that the fieldof use of the invention is not limited to this mode of operation, nor tothe use of acetic acid, but that it comprises all the modifications ofthe softening and iixing treatment by gases or vapours, as set forth inthe preamble to the specication.

We claim:

1. Process for the production of decorative materials from cellulosefibers, consisting in forming a sheet from a suspension of saidcellulose iibers, in producing as the sheet is being formed anaccentuated irregular distribution of the bers in the sheet forobtaining marbling, veins and the like consisting of sheet portions inwhich the bers are thickened or more closely set, in treating the sheetin a gumming bath comprising a solution of gelatine, to which asubstance containing SiOz has been added, and thereupon in a fixing bathcontaining lformaldehyde and castor oil.

2. Process for the production of decorative materials from cellulosefibers, consisting in forming a sheet on a paper making machine from adilute solution of said fibers to which a linseed decoction has beenadded while vibrating the wire of the machine suiciently to produce anirregular accentuated distribution of the ilbers for the purpose ofobtaining marbling, veins and they-like. treating the sheet thus formedin a gumming bath comprising a gelatine solution to which a substancecontaining SiOz has been added and in treating the sheet in a xing bathcontaining formaldehyde and castor oil.

3. Process for the production of decorative materials from cellulosefibers, consisting in forming a sheet on a paper machine from asuspension of said cellulose fibers, in drying the sheet, in winding andtwisting said sheet so as to obtain thereon a plurality of zones havinga smaller resistance to penetration of a liquid, in treating said sheetin a gumming bath comprising a gelatine solution to which a substancecontaining SiO2 has been added and thereupon in a iixing bat-hcontaining formaldehydeand castor oil.

4. Process for the production of decorative materials from celluloseiibers, consisting in forming a sheet on a paper machine from asuspension of said cellulose fibers, in treating said sheet with anastringent solution, in rapidly drying said sheet so as to causeshrinkage thereof, in winding and twisting said sheet so as to formthereon a plurality of zones having a smaller resistance to liquidpenetration, in treating the sheet in a gumming bath comprising agelatine solution to which a substance containing SiOz has been addedand in treating the sheet in a xing bath containing formaldehyde andcastor oil.

5. Process for the production of decorativematerials obtained fromcellulose ilbers, consisting in continuously forming a sheet on a papermaking machine from a dilute suspension of said fibers to which adecoction of linseed has been added, in producing as thel sheet is beingformed an irregular accentuated distribution of the fibers by lateralvibrations of the wire of the paper machine, for the purpose ofobtaining veins, marbling and the like, in treating said sheet with anastringent solution, in rapidly drying said sheet so as to cause same toshrink and crumplc, in winding and twisting said sheet so as to formthereon a plurality of zones having a smaller resistance-to liquidpenetration, in treating said sheet in agumming bath comprising agelatine solution to which a substance containing SiOz has been addedand in treating said sheet in a iixing bath containing formaldehyde andcastor oil.

6. Process for the production of decorative materials -from cellulosefibers consisting in forming a sheet from a suspension of said bers, inproducing as the sheet is being formed an accentuated irregulardistribution of the fibers in the sheet, for the purpose o1' obtainingveins, marbling and the like consisting of sheet portions in which thefibers are thickened, in treating the sheet in a gumming bath comprisinga gelatine solution to which a substance SiO'.- has been added, the SiOzquantity not exceeding that contained in a one percent solution ofsilicate of sodium having the same volume as the gumming bath and intreating said sheet in a ilxing bath containing potassium bichromate andcastor oil.

7. Process for the production of decorative materials from celluloseiibers consisting in forming a sheet from a suspension of said ibers, inproducing during the sheet formation an accen tuated irregulardistribution of the fibers in the sheet for the purpose of obtainingveins, marbling and the like, consisting of sheet portions in which thefibers are thickened, in treating the sheet in a gumming bath comprising100 liters water, 25 kgs. gelatine, labout 500 grams sodium silicate,200 grams aluminium sulphate and in treating said sheet in a xing bath.

8. Process for the production of decorative materials obtained fromcellulose fibers, consisting in forming a sheet from a suspension ofsaid fibers, in producing as the sheet is being formed, an accentuatedirregular distribution oi the iibers in the sheet for the purpose ofobtaining veins, marbling and the like consisting of sheet portions inwhich the fibers are more closely set, in subjecting the sheets thusformed to a softening operation by means of a gaseous iuid, in treatingsaid sheet in a gumming bath consisting of a gelatine solution to whicha substance containing SiOz has been added and thereupon in a xing bathcontaining formaldehyde and castor oil.

9. Process for the production of decorative materials from cellulosefibers, consisting in forming a sheet on a paper making machine from adilute suspension of said iibers. to which a decoction of linseed hasbeen added, in producing an irregular accentuated distribution of theiibers by lateral vibrations of the wire of said machine, for thepurpose of forming veins, marbling and the like, in subjecting thesheets thus obtained to a softening operation by means oi' a gaseousiiuid, in treating the sheet in a gumming bath comprising a gelatinesolution to which a substance containing SiOa has been added andthereupon in a xing bath containing formaldehyde and castor oil.

10. Process for the production of decorative materials from cellulosebers, consisting in forming a sheet on a paper machine from a dilutesuspension of said fibers, to which a decoction of linseed has beenadded, in producing as the sheet is being formed an irregularaccentuated distribution of the fibers by lateral vibrations of the wireof said machine for the purpose of obtaining veins, marbling and thelike, in treating said sheet with an astringent solution, in rapidlydrying said sheet so as to obtain shrinkage and cruinpling thereof, inwinding and twisting said sheet so as to obtain thereon a plurality ofzones having a smaller resistance to liquid penetra;

tion, in immersing said sheet into a dye solution so yas to form thereonfurther veins, marbling and the like, in submitting the: sheets thusobtained to a. softening operation by means of a gaseous fluid, intreating the sheet in a gumming bath comprising a gelatine solution towhich a substance containing SiOz has been added, and thereupon in afixing bath containing formaldehyde and castor oil.

11. Process for the production of decorative materials from cellulosebers. consisting in forming a sheet from a suspension of said cellulosefibers, in producing as the sheet is being formed an accentuatedirregular distribution of the bers in the sheet for obtaining marbling,veins and the like consisting of sheet portions in which the fibers arethickened or more closely set, in treating the sheet in a gumming bathcomprising a solution of gelatine, to which a substance containing SiOzhas been added, and thereupon in a xing bath containing formaldehyde andcastor oil to which a softening substance, such as.

glycerine, has been added.

12. Process for the production of decorative materials from cellulosefibers, consisting in forming a sheet from a suspension of saidcellulose fibers, in producing as the sheet is being formed anaccentuated irregular distribution of the bers in the sheet forobtaining marbling, veinsand the like consisting of sheet portions inwhich the fibers are thickened or more closely set, in treating thesheet in a gumming bath comprising a solution of gelatine to which aquantity of SiO: has been added such that it does not exceed thatcontained in a one percent solution of sodium silicate having the samevolume as the gumming' bath with the simultaneous addition of softeningsubstances, such as glycerine.

13. Decorative material which comprises a sheet of irregularly feltedcellulose bers, said bers being disposed to form marbling, veins andlike eects.

14. Decorative sheet material which comprises a cellulosic fibrous basein which the fibers are irregularly disposed to form marbling, veins andlike etects, said base carrying an intimate reinforcing coating of acoagulated gelatinous character containing a material including thegroup SiOz.

15. Decorative sheet material which comprises irregularly felted paperimpregnated with a hardened gelatine composition containing an alkalimetal silicate.

16. Decorative colored sheet material which comprises a member of thegroup consisting of paper and irregularly felted paper, impregnated witha hardened gelatinous composition containing a member of the groupconsisting of alkali metal silicates and silicio acid.

VALENTINO BOSSO. NICOLO SILVESTRINI. FRANCESCO SACCHI.

